Organic metal complex, and polymer, mixture, composition and organic electronic device containing same and use thereof

ABSTRACT

An organic metal complex as shown by general formula (I) or (II), wherein the ring containing Ar1 is preferably a N-hetero six-membered aromatic ring, and a polymer, a mixture, a composition and an organic electronic device comprising the complex and a use thereof. The organic electronic device, particularly an organic light emitting diode, and the use thereof in display and illumination technologies. By optimizing the device structure and changing the concentration of the metal complex in a matrix, the best performances of the device can be attained, an OLED device with a high efficiency, high luminance and high stability is achieved, and a relatively good material option is provided for full-colour display and illumination applications.

TECHNICAL FIELD

The present disclosure relates to an organic metal complex containingN-hetero-six-membered ring as a new ligand, and a polymer, a mixture, aformulation, an organic electronic device comprising the same andapplication thereof. In addition, the present disclosure further relatesto an organic electronic device comprising the organic metal complex, inparticular to an organic light emitting diode, and its use in displayand lighting technology.

BACKGROUND

Organic light-emitting diode (OLED) has showed great potential inapplications of optoelectronic devices (such as flat-panel displays andlighting) because of the synthetic diversity, relatively lowmanufacturing costs, and excellent optical and electrical properties oforganic semiconductive materials.

In order to improve the emitting efficiency of organic light-emittingdiode, various light emitter materials based on fluorescent andphosphorescent materials have been developed. Organic light-emittingdiodes using fluorescent materials are characterized by highreliability, but their internal electroluminescence quantum efficiencyis limited to 25% under electric field excitation, since the probabilityratio of the exciton to singlet excited state and triplet excited stateis 1:3. In 1999, Professor Thomson of the University of SouthernCalifornia and Professor Forrest of Princeton University incorporatedtris (2-phenylpyridine) iridium Ir (ppy)₃ into N, N-dicarbazole biphenyl(CBP), to successfully prepare green electroluminescent devices, whicharoused great interest in complex phosphorescent materials. Theintroduction of heavy metals improves the molecular spin orbit coupling,shortens the phosphorescence life and enhances the intersystem crossingof molecules, so that phosphorescence can be successfully launched.Further reactions of this kind of complex are mild, thus it is easy tochange the complex structure and the substituent group, to adjust theemission wavelength, and thus get the excellent performance of theelectroluminescent material. So far, the internal quantum efficiency ofphosphorescent OLED is close to 100%. However, the stability ofphosphorescent OLED needs to be improved. The stability of thephosphorescent OLED depends largely on the luminous body itself. Most ofthe widely used iridium and platinum metal complexes are mostly confinedto the five-membered ring ligands, while the six-membered ring ligandswith structural stability are less. In order to further improve thematerial properties and broaden the phosphorescent metal complexes, itis urgently needed to develop highly efficient phosphorescent metalcomplexes containing new ligands.

SUMMARY

In view of the above-mentioned deficiencies of the prior art, it is anobject of the present disclosure to provide an N-hetero-six-memberedring organic metal complex, which can effectively improve the stabilityof the complex material, luminous efficiency and the performance of thecorresponding device since the six-membered ring ligands have excellentrigidity, chemical and thermal stability.

A technical solution for achieving the above object is an organic metalcomplex having a structure of the general formula (I) or (II):

wherein,

X is a bridging group, and when n>1, each X is the same or differentbridging group, X being linked to Ar³ or Ar² by a single bond or adouble bond, and X is selected from the group consisting of a singlebond, N(R¹), B(R¹), C(R¹)₂, O, Si(R¹)₂, C═C(R¹)₂, S, S═O, SO₂, P(R¹) andP(═O)R¹;

each R¹ is the same or different from one another in multipleoccurrences, and R¹ is selected from the group consisting of H; F; Cl;Br; I; D; CN; NO₂; CF₃; B(OR²)₂; Si(R²)₃; straight-chain alkanes; alkaneethers; alkane thioethers, branched alkanes or cycloalkanes containing 1to 10 carbon atoms; and alkane ethers or alkane thioether groupscontaining 3 to 10 carbon atoms; each R¹ group is substituted with oneor more active groups R², and one or more non-adjacent methylene groups(CH₂) are optionally substituted by any one selected from the groupconsisting of R²C═CR², C═C, Si(R²)₂, Ge(R²)₂, Sn(R²)₂, C═O, C═S, C═Se,C═N(R²), O, S, —COO— and CONR²; wherein one or more H can be substitutedby D, F, Cl, Br, I, CN or N₂; or by an aromatic amine substituted by oneor more R² or one aromatic group or heteroaromatic group; or by asubstituted or unsubstituted carbazole.

Each R² is the same or different from each other in multipleoccurrences, and is selected from the group consisting of H, D, analiphatic alkane having 1 to 10 carbons atoms, an aromatic hydrocarbon,and a substituted or unsubstituted aromatic ring or heteroaromatic grouphaving 5 to 10 carbon atoms.

Each of Ar¹-Ar³ is the same or different from each other in multipleoccurrence, and is an unsubstituted or a R¹-substituted aromatichydrocarbon or heteroaromatic cylic hydrocarbon system;

is a bidentate ligand.

M is a transitional metal element.

m and n are respectively any one of numbers 1-3.

In some embodiments, the organic metal complex is preferably selectedfrom the following general formulas:

wherein each of R³, R⁴, R⁵ and R⁶ independently represents any oneselected from the group consisting of —H; —F; —Cl; Br; I; -D; —CN; —NO₂;—CF₃; B(OR²)₂; Si(R²)₃; straight-chain alkane; alkane ether; alkanethioether, branched alkane, or cycloalkane containing 1 to 10 carbonatoms; alkane ether or alkane thioether group containing 3 to 10 carbonatoms; and aryl group containing 6 to 10 carbon atoms.

In some embodiments, M is selected from any one transition metal of thegroup consisting of Cr, Mo, W, Ru, Rh, Ni, Ag, Cu, Zn, Pd, Au, Os, Re,Ir and Pt. In a preferred embodiment, M is selected from Ir or Pt.

In some embodiment,

is N-hetero-six-membered ring unit, and is independently selected fromgeneral formulas C1 to C4 in multiple occurrences:

wherein each of R⁷ to R⁹ independently represents any one selected fromthe group consisting of —H; —F; —Cl; Br; I; -D; —CN; —NO₂; —CF₃;B(OR²)₂; Si(R²)₃; straight-chain alkane; alkane ether; alkane thioether,branched alkane or cycloalkane containing 1 to 10 carbon atoms; alkaneether or alkane thioether group containing 3 to 10 carbon atoms, andaryl group containing 6 to 10 carbon atoms.

In some embodiments,

is a single anion ligand, and is independently selected from thefollowing general formulas L1 to L15 in multiple occurrences:

wherein each of R⁶⁰ to R¹²⁹ independently represents any one selectedfrom the group consisting of —H; —F; —Cl; Br; I; -D; —CN; —NO₂; —CF₃;B(OR²)₂; Si(R²)₃; straight-chain alkane; alkane ether; alkane thioether,branched alkane or cycloalkane containing 1 to 10 carbon atoms; alkaneether or alkane thioether group containing 3 to 10 carbon atoms, andaryl group containing 6 to 10 carbon atoms, wherein the dashed lineindicates connecting with the metal element M in the form of a singlebond.

Another object of the present disclosure is to provide a polymercomprising a repeating unit containing a structural unit represented bythe general formula (I) or (II).

Another object of the present disclosure is to provide a mixturecomprising the organic metal complex of the present disclosure and atleast one organic functional material. The organic functional materialcan be any one selected from the group consisting of a hole-injectingmaterial, a hole-transporting material, an electron-transportingmaterial, an electron-injecting material, an electron-blocking material,a hole-blocking material, a light emitter material, and a host materialetc.

Another object of the present disclosure is to provide a formulationcomprising the organic metal complex or the polymer, and at least oneorganic solvent.

Another object of the present disclosure is to provide an use of theorganic metal complex in an organic electronic device.

Another object of the present disclosure is to provide an organicelectronic device comprising the organic metal complex or the polymer orthe mixture thereof.

In some embodiments, the organic electronic device is any one selectedfrom the group consisting of: organic light emitting diode (OLED),organic photovoltaic cell (OPV), organic light emitting electrochemicalcell (OLEEC), organic field effect transistor (OFET), organic lightemitting field effect transistor, organic laser, organic spintronicdevice, organic sensor and organic plasmonic emitter diode.

DETAILED DESCRIPTION OF THE EMBODIMENTS

The present disclosure provides an organic metal complex containingN-hetero-six-membered ring and corresponding organic mixture, andapplication in the organic electronic device. The present disclosurewill now be described in greater detail so that the purpose, technicalsolutions, and technical effects thereof are more clear andcomprehensible. It is to be understood that the specific embodimentsdescribed herein are merely illustrative of, and are not intended tolimit, the disclosure.

The present disclosure relates to an organic metal complex representedby the following general formula (I) or (II):

Wherein, X is the same or different bridging group in each occurrence,and they are linked to Ar¹ or Ar² by a single bond or a double bond, andselected from the group consisting of a single bond, N(R¹), B(R¹),C(R¹)₂, O, Si(R¹)₂, C═C(R¹)₂, S, S═O, SO₂, P(R¹) and P(═O)R¹;

each R¹ is the same or different from one another in multipleoccurrences, and R¹ is selected from the group consisting of H; F; Cl;Br; I; D; CN; NO₂; CF₃; B(OR²)₂; Si(R²)₃; straight-chain alkanes; alkaneethers; alkane thioethers, branched alkanes or cycloalkanes containing 1to 10 carbon atoms; and alkane ethers or alkane thioether groupscontaining 3 to 10 carbon atoms; each R¹ group is substituted with oneor more active groups R², and one or more non-adjacent methylene groups(CH₂) are optionally substituted by any one selected from the groupconsisting of R²C═CR², C═C, Si(R²)₂, Ge(R²)₂, Sn(R²)₂, C═O, C═S, C═Se,C═N(R²), O, S, —COO— and CONR²; wherein one or more H can be substitutedby D, F, Cl, Br, I, CN or N₂; or by an aromatic amine substituted by oneor more R² or one aromatic group or heteroaromatic group; or by asubstituted or unsubstituted carbazole.

Each R² is the same or different from each other in each occurrence, andis selected from the group consisting of H, D, an aliphatic alkanehaving 1 to 10 carbons atoms, an aromatic hydrocarbon, and a substitutedor unsubstituted aromatic ring or a heteroaromatic group having 5 to 10carbon atoms;

Each of Ar¹-Ar³ is the same or different from each other in eachoccurrence, and is an unsubstituted or a R¹-substituted aromatichydrocarbon or heteroaromatic cylic hydrocarbon system;

is a bidentate ligand.

M is a transitional metal.

m is any one of numbers 0-3, and n is any one of numbers 1-3.

In one preferred embodiment, the organic metal complex of presentdisclosure is selected from the following general formulas:

wherein each of R³, R⁴, R⁵ and R⁶ independently represents any oneselected from the group consisting of —H; —F; —Cl; Br; I; -D; —CN; —NO₂;—CF₃; B(OR²)₂; Si(R²)₃; straight-chain alkane; alkane ether; alkanethioether, branched alkane, or cycloalkane containing 1 to 10 carbonatoms; alkane ether or alkane thioether group containing 3 to 10 carbonatoms; and aryl group containing 6 to 10 carbon atoms.

Wherein,

is N-hetero-six-membered ring unit, and is independently selected fromgeneral formulas C1 to C4 in multiple occurrences:

wherein each of R¹ to R⁹ independently represents any one selected fromthe group consisting of —H; —F; —Cl; Br; I; -D; —CN; —NO₂; —CF₃;B(OR²)₂; Si(R²)₃; straight-chain alkane; alkane ether; alkane thioether,branched alkane or cycloalkane containing 1 to 10 carbon atoms; alkaneether or alkane thioether group containing 3 to 10 carbon atoms, andaryl group containing 6 to 10 carbon atoms.

Wherein

is a single anion ligand.

In some preferred embodiments, the single anion ligand is independentlyselected from the following general formulas L1 to L15 in multipleoccurrences:

wherein each of R⁶⁰ to R¹²⁹ independently represents any one selectedfrom the group consisting of —H; —F; —Cl; Br; I; -D; —CN; —NO₂; —CF₃;B(OR²)₂; Si(R²)₃; straight-chain alkane; alkane ether; alkane thioether,branched alkane or cycloalkane containing 1 to 10 carbon atoms; alkaneether or alkane thioether group containing 3 to 10 carbon atoms, andaryl group containing 6 to 10 carbon atoms, wherein the dashed lineindicates connecting with the metal element M in the form of a singlebond.

In the organic metal complex of the present disclosure, M is atransition metal element.

In one preferred embodiment, M is any one selected from the groupconsisting of Cr, Mo, W, Ru, Rh, Ni, Ag, Cu, Zn, Pd, Au, Os, Re, Ir andPt. In one particularly preferred embodiment, M is selected from Ir orPt.

From the viewpoint of the heavy atom effect, Ir or Pt is preferably usedas the central metal M of the above-mentioned metal organic complex.Iridium is particularly preferred, since iridium is chemically stableand has a significant heavy atom effect that results in high luminousefficiency.

Specific examples of suitable metal organic complexes according to thepresent disclosure are given below, but the present disclosure is notlimited to these metal complexes:

The organic metal complex of the present disclosure has a light emissionwavelength between 300 and 1000 nm, preferably between 350 and 900 nm,and more preferably between 400 and 800 nm.

The present disclosure further relates to a polymer, wherein at leastone repeating unit contains a structure of the general formula (I) or(II). In some embodiment, the polymer may be non-conjugated polymers inwhich the structure unit represented by the general formula (I) or (II)is on the side chain. In another preferred embodiment, the polymer isconjugated polymers.

The present disclosure further relates to a mixture comprising theorganic metal complex or the mixture of the present disclosure, and atleast one of the other organic functional materials.

The other organic functional materials includes hole (also referred toas electron hole) injecting or transport material (HIM/HTM),hole-blocking material (HBM), electron-injection or transport material(EIM/ETM), electron-blocking material (EBM), organic host material(Host), singlet emitter (fluorescent emitter), multiplet emitter(phosphorescent emitter), especially light-emitting organic metalcomplexes. Non-limiting examples of various organic functional materialsare described, for example, in WO2010135519A1, US20090134784A1, and WO2011110277A1, whole contents of which are incorporated herewith byreference.

The organic functional material may be a small-molecule polymericmaterial.

As used herein, the term “small molecule” refers to a molecule that isnot a polymer, an oligomer, a dendrimer, or a blend. In particular,there is no repetitive structure in small molecules. The molecularweight of the small molecule is no greater than 3000 g/mole, morepreferably no greater than 2000 g/mole, and most preferably no greaterthan 1500 g/mole.

As used herein, the term “polymer” includes homopolymer, copolymer, andblock copolymer. In addition, in the present disclosure, the polymeralso includes dendrimer. The synthesis and application of dendrimers aredescribed in Dendrimers and Dendrons, Wiley-VCH Verlag GmbH & Co. KGaA,2002, Ed. George R. Newkome, Charles N. Moorefield, Fritz Vogtle.

The term “conjugated polymer” as defined herein is a polymer whosebackbone is predominantly composed of the sp² hybrid orbital of carbon(C) atom. Some known non-limiting examples are: polyacetylene and poly(phenylene vinylene), on the backbone of which the C atom can also beoptionally substituted by other non-C atoms, and which is stillconsidered to be a conjugated polymer when the sp² hybridization on thebackbone is interrupted by some natural defects. In addition, theconjugated polymer in the present disclosure may also comprise aromaticamine, aryl phosphine and other heteroarmotics, organic metal complexes,and the like.

In the present disclosure, the host material, the matrix material, Hostmaterial and Matrix material have the same meaning and areinterchangeable.

In the present disclosure, the metal organic complex and the organicmetal complex have the same meaning and are interchangeable.

The organic functional material is described in detail in the following(but not limited thereto).

1. HIM/HTM/EBM

Suitable organic HIM/HTM materials may include any one of the compoundshaving the following structural units: phthalocyanines, porphyrins,amines, aromatic amines, biphenyl triaromatic amines, thiophenes,thiophenes such as dithiophenethiophene and thiophthene, pyrrole,aniline, carbazole, indeno-fluorene, and derivatives thereof. Othersuitable HIMs also include: fluorocarbon-containing polymers; polymerscontaining conductive dopants; conductive polymers such as PEDOT/PSS;self-assembled monomers such as compounds containing phosphonic acid andsilane derivatives; metal oxides, such as MoOx; metal complex, and acrosslinking compound, and the like.

The electron blocking layer (EBL) is typically used to block electronsfrom adjacent functional layers, particularly light emitting layers. Incontrast to a light-emitting device without a blocking layer, thepresence of EBL usually results in an increase in luminous efficiency.The electron blocking layer (EBL) of the electron blocking material(EBM) requires a higher LUMO than that of the adjacent functional layer,such as the light emitting layer. In a preferred embodiment, the EBM hasa greater energy level of excited state than that of the adjacent lightemitting layer, such as a singlet or triplet level, depending on theemitter. In another preferred embodiment, the EBM has a hole transportfunction. HIM/HTM materials, which typically have high LUMO levels, canbe used as EBM.

Other examples of cyclic aromatic amine derivative compounds that may beused as HTM or HIM may include, but are not limited to, the generalstructure as follows:

wherein each Ar¹ to Ar⁹ may be independently selected from the groupconsisting of: cyclic aromatic hydrocarbon compounds such as benzene,biphenyl, triphenyl, benzo, naphthalene, anthracene, phenalene,phenanthrene, fluorene, pyrene, chrysene, perylene, azulene; andaromatic heterocyclic compounds such as dibenzothiophene, dibenzofuran,furan, thiophene, benzofuran, benzothiophene, benzoselenophene,carbazole, pyrazole, imidazole, triazole, isoxazole, thiazole,oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine,pyrimidine, pyrazine, triazine, oxazine, oxathiazin, oxadiazine, indole,benzimidazole, indoxazine, bisbenzoxazole, benzisoxazole, benzothiazole,quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline,naphthalene, phthalein, pteridine, xanthene, acridine, phenazine,phenothiazine, phenoxazine, dibenzoselenophene, benzoselenophene,benzofuropyridine, indolocarbazole, pyridylindole, pyrrolodipyridine,furodipyridine, benzothienopyridine, thienodipyridine,benzoselenophenopyridine, and selenophenodipyridine; groups containing 2to 10 membered ring structures which may be the same or different typesof aromatic cyclic or aromatic heterocyclic groups and are bonded toeach other directly or through at least one of the following groups, forexample: oxygen atom, nitrogen atom, sulfur atom, silicon atom,phosphorus atom, boron atom, chain structure unit, and aliphatic cyclicgroup; and wherein each Ar may be further optionally substituted, andthe substituents may optionally be hydrogen, alkyl, alkoxy, amino,alkene, alkyne, aralkyl, heteroalkyl, aryl and heteroaryl.

In one aspect, Ar¹ to Ar⁹ may be independently selected from the groupsof the group consisting of:

wherein n is an integer of 1 to 20; X¹ to X⁸ are CH or N; Ar1 is asdefined above.

Additional non-limiting examples of cyclic aromatic amine derivativecompounds may be found in U.S. Pat. Nos. 3,567,450, 4,720,432,3,615,404, and 5,061,569.

Examples of metal complexes that can be used as HTM or HIM include, butnot limited to, the following general structures:

M is a metal, having an atomic weight greater than 40;

(Y¹-Y²) is a bidentate ligand, wherein Y¹ and Y² are independentlyselected from the group consisting of C, N, O, P, and S; L is anauxiliary ligand; m is an integer from 1 to the maximum coordinationnumber of the metal; m+n is the maximum coordination number of themetal.

In one embodiment, (Y¹-Y²) may be a 2-phenylpyridine derivative.

In another embodiment, (Y¹—Y²) may be a carbene ligand.

In another embodiment, M may be selected from the group consisting ofIr, Pt, Os, and Zn.

In another aspect, the HOMO of the metal complex that can be used as HTMor HIM is greater than −5.5 eV (relative to the vacuum level).

Examples of a suitable HIM/HTM/EBM compound are listed below

2. EIM/ETM/HBM

Examples of EIM/ETM material are not particularly limited, and any metalcomplex or organic compound may be used as EIM/ETM as long as they cantransfer electrons. Preferred organic EIM/ETM materials may be selectedfrom the group consisting of tris (8-quinolinolato) aluminum (AlQ3),phenazine, phenanthroline, anthracene, phenanthrene, fluorene,bifluorene, spiro-bifluorene, phenylene-vinylene, triazine, triazole,imidazole, pyrene, perylene, trans-indenofluorene, cis-indenonfluorene,dibenzol-indenofluorene, indenonaphthalene, benzanthracene and theirderivatives.

The hole-blocking layer (HBL) is typically used to block holes fromadjacent functional layers, particularly light-emitting layers. Incontrast to a light-emitting device without a blocking layer, thepresence of HBL usually leads to an increase in luminous efficiency. Thehole-blocking material (HBM) of the hole-blocking layer (HBL) requires alower HOMO than that of the adjacent functional layer, such as thelight-emitting layer. In a preferred embodiment, the HBM has a greaterenergy level of excited state than that of the adjacent light-emittinglayer, such as a singlet or triplet, depending on the emitter. Inanother preferred embodiment, the HBM has an electron-transportfunction. Typically, EIM/ETM materials with deep HOMO levels may be usedas HBM.

In another aspect, compounds that may be used as EIM/ETM/HBM compoundsmay be molecules comprising at least one of the following groups:

wherein R¹ may be selected from the group consisting of: hydrogen,alkyl, alkoxy, amino, alkene, alkyne, aralkyl, heteroalkyl, aryl andheteroaryl, wherein, when they are aryl or heteroaryl, they may have thesame meaning as Ar¹ and Ar² in HTM as described above; Ar¹-Ar⁵ may havethe same meaning as Ar¹ in HTM as described above; n is an integer from0 to 20; and X¹-X⁸ may be selected from CR¹ or N.

On the other hand, examples of metal complexes that may be used asEIM/ETM may include, but are not limited to, the following generalstructure:

(O—N) or (N—N) is a bidentate ligand, wherein the metal coordinates withO, N, or N, N; L is an auxiliary ligand; and m is an integer whose valueis from 1 to the maximum coordination number of the metal.

An example of a suitable ETM compound is listed below:

In another preferred embodiment, the organic alkali metal compound maybe used as the EIM. In the present disclosure, the organic alkali metalcompound may be understood as a compound having at least one alkalimetal, i.e., lithium, sodium, potassium, rubidium, and cesium, andfurther comprising at least one organic ligand.

Suitable organic alkali metal compounds include the compounds describedin U.S. Pat. No. 7,767,317 B2, EP 1941562B1 and EP 1144543B1.

The preferred organic alkali metal compound may be a compound of thefollowing formula:

wherein R¹ has the same meaning as described above, and the arcrepresents two or three atoms and the bond to form a 5- or 6-memberedring with metal M when necessary, while the atoms may be optionallysubstituted by one or more R¹; and wherein M is an alkali metal selectedfrom the group consisting of lithium, sodium, potassium, rubidium, andcesium.

The organic alkali metal compound may be in the form of a monomer, asdescribed above, or in the form of an aggregate, for example, two alkalimetal ions with two ligands, four alkali metal ions and four ligands,six alkali metal ions and six ligands, or in other forms.

The preferred organic alkali metal compound may be a compound of thefollowing formula:

wherein, the symbols used are as defined above, and in addition:

o, it may be the same or different in each occurrence, selected from 0,1, 2, 3 or 4; and

p, it may be the same or different in each occurrence, selected from 0,1, 2 or 3.

In a preferred embodiment, the alkali metal M is selected from the groupconsisting of lithium, sodium, potassium, more preferably lithium orsodium, and most preferably lithium.

In a preferred embodiment, the electron-injection layer includes theorganic alkali metal compound, and more preferably theelectron-injection layer consists of the organic alkali metal compound.

In another preferred embodiment, the organic alkali metal compound isdoped into other ETMs to form an electron-transport layer or anelectron-injection layer, more preferably an electron-transport layer.

Examples of a suitable organic alkali metal compound are listed below:

3. Triplet Host Materials

Examples of a triplet host material are not particularly limited and anymetal complex or organic compound may be used as the host material aslong as its triplet energy is greater than that of the emitter,especially a triplet emitter or phosphorescent emitter.

Examples of metal complexes that may be used as triplet hosts mayinclude, but are not limited to, the general structure as follows:

wherein M is a metal; (Y³-Y⁴) may be a bidentate ligand, Y³ and Y⁴ maybe independently selected from the group consisting of C, N, O, P, andS; L is an auxiliary ligand; m is an integer with the value from 1 tothe maximum coordination number of the metal; and, m+n is the maximumnumber of coordination of the metal.

In a preferred embodiment, the metal complex which may be used as thetriplet host has the following form:

(O—N) is a bidentate ligand in which the metal is coordinated to O and Natoms.

In one embodiment, M may be selected from Ir and Pt.

Examples of organic compounds that may be used as triplet host areselected from the group consisting of: compounds containing cyclicaromatic hydrocarbon groups, such as benzene, biphenyl, triphenyl,benzo, and fluorene; compounds containing aromatic heterocyclic groups,such as triphenylamine, dibenzothiophene, dibenzofuran,dibenzoselenophen, furan, thiophene, benzofuran, benzothiophene,benzoselenophene, carbazole, indolocarbazole, indolopyridine,pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole,oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine,pyrimidine, pyrazine, triazine, oxazine, oxathiazin, oxadiazine, indole,benzimidazole, indoxazine, bisbenzoxazole, isoxazole, benzothiazole,quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline,naphthalene, phthalein, pteridine, xanthene, acridine, phenazine,phenothiazine, phenoxazine, benzofuropyridine, furodipyridine,benzothienopyridine, thienodipyridine, benzoselenophenopyridine, andselenophenodipyridine, or a combination thereof; groups containing 2 to10 membered ring structures which may be the same or different types ofaromatic cyclic or aromatic heterocyclic groups and are bonded to eachother directly or through at least one of the following groups, forexample: oxygen atom, nitrogen atom, sulfur atom, silicon atom,phosphorus atom, boron atom, chain structure unit, and aliphatic cyclicgroup; and wherein each Ar may be further optionally substituted, andthe substituents may optionally be hydrogen, alkyl, alkoxy, amino,alkene, alkyne, aralkyl, heteroalkyl, aryl and heteroaryl.

In a preferred embodiment, the triplet host material may be selectedfrom compounds comprising at least one of the following groups:

R¹-R⁷ may be independently selected from the group consisting ofhydrogen, alkyl, alkoxy, amino, alkene, alkyne, aralkyl, heteroalkyl,aryl and heteroaryl, which may have the same meaning as Ar¹ and Ar²described above when they are aryl or heteroaryl; n may be an integerfrom 0 to 20; X¹-X⁸ may be selected from CH or N; and X⁹ may be selectedfrom CR¹R2 or NR1. R¹, R² have the same definition of R¹ in the ETMsection.

Examples of suitable triplet host material are listed below:

4. Singlet Host Material:

Examples of singlet host material are not particularly limited and anyorganic compound may be used as the host as long as its singlet stateenergy is greater than that of the emitter, especially the singletemitter or fluorescent emitter.

Non-limiting examples of organic compounds used as singlet hostmaterials may be selected from the group consisting of: compoundscontaining cyclic aromatic hydrocarbon groups, such as benzene,biphenyl, triphenyl, benzo, naphthalene, anthracene, phenalene,phenanthrene, fluorene, pyrene, chrysene, perylene, azulene; aromaticheterocyclic compounds, such as triphenylamine, dibenzothiophene,dibenzofuran, dibenzoselenophen, furan, thiophene, benzofuran,benzothiophene, benzoselenophene, carbazole, indolocarbazole,indolopyridine, pyrrolodipyridine, pyrazole, imidazole, triazole,isoxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole,pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine,oxathiazin, oxadiazine, indole, benzimidazole, indoxazine,bisbenzoxazole, isoxazole, benzothiazole, quinoline, isoquinoline,cinnoline, quinazoline, quinoxaline, naphthalene, phthalein, pteridine,xanthene, acridine, phenazine, phenothiazine, phenoxazine,benzofuropyridine, furodipyridine, benzothienopyridine,thienodipyridine, benzoselenophenopyridine, and selenophenodipyridine;and groups comprising 2 to 10 membered ring structures, which may be thesame or different types of aromatic cyclic or aromatic heterocyclicgroups and are linked to each other directly or by at least one of thefollowing groups, such as oxygen atom, nitrogen atom, sulfur atom,silicon atom, phosphorus atom, boron atom, chain structure unit, andaliphatic rings.

In a preferred embodiment, the singlet host material may be selectedfrom compounds comprising at least one of the following groups:

R¹ may be independently selected from the group consisting of hydrogen,alkyl, alkoxy, amino, alkene, alkyne, aralkyl, heteroalkyl, aryl andheteroaryl; Ar¹ is aryl or heteroaryl and has the same meaning as Ar¹defined in the HTM above; n is an integer from 0 to 20; X¹-X⁸ isselected from CH or N; X⁹ and X¹⁰ are selected from CR¹R² or NR¹.

Examples of a suitable singlet host material are listed below:

5. Singlet Emitter

The singlet emitter tends to have a longer conjugate π-electron system.To date, there have been many examples, such as, but not limited to,styrylamine and derivatives thereof disclosed in JP2913116B andWO2001021729A1, and indenofluorene and derivatives thereof disclosed inWO2008/006449 and WO2007/140847.

In a preferred embodiment, the singlet emitter may be selected from thegroup consisting of monostyrylamines, distyrylamines, tristyrylamines,tetrastyrylamines, styrylphosphines, styryl ethers, and arylamines.

Mono styrylamine refers to a compound which comprises an unsubstitutedor optionally substituted styryl group and at least one amine, mostpreferably an aromatic amine. Distyrylamine refers to a compoundcomprising two unsubstituted or optionally substituted styryl groups andat least one amine, most preferably an aromatic amine.Ternarystyrylamine refers to a compound which comprises threeunsubstituted or optionally substituted styryl groups and at least oneamine, most preferably an aromatic amine. Quaternarystyrylamine refersto a compound comprising four unsubstituted or optionally substitutedstyryl groups and at least one amine, most preferably an aromatic amine.Preferred styrene is stilbene, which may be further optionallysubstituted. The corresponding phosphines and ethers are definedsimilarly to amines. Aryl amine or aromatic amine refers to a compoundcomprising three unsubstituted or optionally substituted aromatic cyclicor heterocyclic systems directly attached to nitrogen. At least one ofthese aromatic cyclic or heterocyclic systems is preferably selectedfrom fused ring systems and most preferably has at least 14 aromaticring atoms. Among the preferred examples are aromatic anthramine,aromatic anthradiamine, aromatic pyrene amines, aromatic pyrenediamines, aromatic chrysene amines and aromatic chrysene diamine.Aromatic anthramine refers to a compound in which a diarylamino group isdirectly attached to anthracene, most preferably at position 9. Aromaticanthradiamine refers to a compound in which two diarylamino groups aredirectly attached to anthracene, most preferably at positions 9, 10.Aromatic pyrene amines, aromatic pyrene diamines, aromatic chryseneamines and aromatic chrysene diamine are similarly defined, wherein thediarylarylamino group is most preferably attached to position 1 or 1 and6 of pyrene.

Examples of singlet emitter based on vinylamine and arylamine are alsopreferred examples which may be found in the following patent documents:WO 2006/000388, WO 2006/058737, WO 2006/000389, WO 2007/065549, WO2007/115610, U.S. Pat. No. 7,250,532 B2, DE 102005058557 A1, CN 1583691A, JP 08053397 A, U.S. Pat. No. 6,251,531 B1, US 2006/210830 A, EP1957606 A1, and US 2008/0113101 A1, the whole contents of which areincorporated herein by reference.

Examples of singlet light emitters based on distyrylbenzene and itsderivatives may be found in, for example, U.S. Pat. No. 5,121,029.

Further preferred singlet emitters may be selected from the groupconsisting of: indenofluorene-amine and indenofluorene-diamine such asdisclosed in WO 2006/122630, benzoindenofluorene-amine andbenzoindenofluorene-diamine such as disclosed in WO 2008/006449,dibenzoindenofluorene-amine and dibenzoindenofluorene-diamine such asdisclosed in WO2007/140847.

Other materials useful as singlet emissors include, but not limited to,polycyclic aromatic compounds, especially any one selected from thederivatives of the following compounds: anthracenes such as9,10-di-naphthylanthracene, naphthalene, tetraphenyl, oxyanthene,phenanthrene, perylene such as 2,5,8,11-tetra-t-butylatedylene,indenoperylene, phenylenes such as 4,4′-(bis(9-ethyl-3-carbazovinylene)-1,1′-biphenyl, periflanthene, decacyclene,coronene, fluorene, spirobifluorene, arylpyren (e.g., US20060222886),arylenevinylene (e.g., U.S. Pat. Nos. 5,121,029, 5,130,603),cyclopentadiene such as tetraphenylcyclopentadiene, rubrene, coumarine,rhodamine, quinacridone, pyrane such as 4(dicyanoethylene)-6-(4-dimethylaminostyryl-2-methyl)-4H-pyrane (DCM),thiapyran, bis (azinyl) imine-boron compounds (US 2007/0092753 A1), bis(azinyl) methene compounds, carbostyryl compounds, oxazone, benzoxazole,benzothiazole, benzimidazole, and diketopyrrolopyrrole. Examples of somesinglet emitter materials may be found in the following patentdocuments: U.S. Pat. Nos. 4,769,292, 6,020,078, US 2007/0252517 A1, andUS 2007/0252517 A1, the whole contents of which are incorporated hereinby reference.

Examples of suitable singlet emitters are listed below:

6. Polymers

In some embodiments, the organic functional materials described above,including HIM, HTM, ETM, EIM, Host, fluorescent emitter, andphosphorescent emitters, may be in the form of polymers.

In a preferred embodiment, the polymer suitable for the presentdisclosure is a conjugated polymer. In general, the conjugated polymermay have the general formula:

wherein B, A may be independently selected as the same or differentstructural units in multiple occurrences.

B: a π-conjugated structural unit with relatively large energy gap, alsoreferred to as backbone unit, which may be selected from monocyclic orpolycyclic aryl or heteroaryl, preferably in the form of benzene,biphenylene, naphthalene, anthracene, phenanthrene, dihydrophenanthrene,9,10-dihydrophenanthroline, fluorene, difluorene, spirobifluorene,p-phenylenevinylene, trans-indenofluorene, cis-indenofluorene,dibenzol-indenofluorene, indenonaphthalene and derivatives thereof.

A: a π-conjugated structural unit with relatively small energy gap, alsoreferred to as a functional unit, which, according to differentfunctional requirements, may be selected from the above-mentionedhole-injection or hole-transport material (HIM/HTM), hole-blockingmaterial (HBM), electron-injection or electron-transport material(EIM/ETM), electron-blocking material (EBM), organic host material(Host), singlet emitter (fluorescent emitter), multiplet emitter(phosphorescent emitter).

x,y: >0, and x+y=1.

In a preferred embodiment, the polymer HTM material is a homopolymer,and the preferred homopolymer is selected from the group consisting ofpolythiophene, polypyrrole, polyaniline, polybenzene triarylamine,polyvinylcarbazole and their derivatives.

In another preferred embodiment, the polymer HTM material is aconjugated copolymer represented by Chemical Formula 1, wherein

A: a functional group having a hole transporting capacity, which may beselected from structural units comprising the above-mentionedhole-injection or hole-transport material (HIM/HTM); in a preferredembodiment, A is selected from the group consisting of amine,benzenesulfonates, thiophenes and thiophenes such as dithienothiopheneand thiophene, pyrrole, aniline, carbazole, indolecarbazole,indeno-benzofluorene, pentacene, phthalocyanine, porphyrins and theirderivatives.

x,y: >0, and x+y=1; usually y≥0.10, preferably ≥0.15, more preferably≥0.20, preferably x=y=0.5.

Examples of suitable conjugated polymers that can be used as HTM arelisted below:

wherein R are each independently hydrogen; a straight chain alkyl group,an alkoxy group or a thioalkoxy group having 1 to 20 C atoms; a branchedor cyclic alkyl group, an alkoxy group or a thioalkoxy group or a silylgroup having 3 to 20 C atoms; or a substituted keto group having 1 to 20C atoms; an alkoxycarbonyl group having 2 to 20 C atoms; aryloxycarbonylgroup having 7 to 20 C atoms; a cyano group (—CN); a carbamoyl group(—C(═O)NH₂); a haloyl group (—C(═O)—X wherein X represents a halogenatom); a formyl group (—C(═O)—H); an isocyanato group; an isocyanategroup; a thiocyanate group; an isothiocyanate group; a hydroxyl group; anitro group; a CF₃ group; Cl; Br; F; a crosslinkable group; asubstituted or unsubstituted aromatic or heteroaromatic ring systemhaving 5 to 40 ring atoms; or an aryloxy or heteroaryloxy group having 5to 40 ring atoms, or a combination of these systems in which one or moregroups R may form a single ring or polycyclic aliphatic or aromatic ringsystem between one another and/or with a ring bonded to the group R;

r is 0, 1, 2, 3 or 4;

s is 0, 1, 2, 3, 4 or 5;

x,y: >0, and x+y=1; usually y=y≥0.10, preferably ≥0.15, more preferably≥0.20, preferably x=y=0.5.

Another preferred type of organic ETM material is a polymer having anelectron transporting capacity comprising a conjugated polymer and anonconjugated polymer.

The preferred polymer ETM material is a homopolymer, which is selectedfrom the group consisting ofpolyphenanthrene, polyphenanthroline,polyindenyl fluorene, poly spiethylene fluorene, polyfluorene and theirderivatives.

The preferred polymer ETM material is a conjugated copolymer representedby Chemical Formula 1, wherein A can be independently selected in thesame or different forms in multiple occurrences:

A: a functional group having a electron transporting capacity,preferably selected from the group consisting of tris (8-quinolinolato)aluminum, benzene, biphenylene, naphthalene, anthracene, phenanthrene,dihydrophenanthrene, fluorene, difluorene, spirobifluorene,p-phenylenevinylene, pyrene, perylene, 9,10-dihydrophenanthroline,phenoxazine, phenanthroline, trans-indenofluorene, cis-indenonfluorene,dibenzol-indenofluorene, indenonaphthalene, benzanthracene and theirderivatives.

x,y: >0, and x+y=1; usually y≥0.10, preferably ≥0.15, more preferably≥0.20, preferably x=y=0.5.

In a preferred embodiment, light-emitting polymers are conjugatedpolymers having the following formula:

B: as defined in chemical formula 1.

A1: a functional group having a hole or electron transporting capacity,which may be selected from structural units of the above-mentionedhole-injection or hole-transport material (HIM/HTM), or electroninjection or transport material.

A2: a group having light emitting function, which may be selected fromstructural units of singlet emitter (fluorescent emitter) or multipletemitter (phosphorescent emitter).

x,y,z: >0, and x+y+z=1;

Examples of light-emitting polymers are disclosed in the followingpatent applications: WO2007043495, WO2006118345, WO2006114364,WO2006062226, WO2006052457, WO2005104264, WO2005056633, WO2005033174,WO2004113412, WO2004041901, WO2003099 901, WO2003051092, WO2003020790,US20040076853, US20040002576, US2007208567, U.S. Pat. No. 5,962,631,EP201345477, EP20031344788 and DE102004020298, the whole contents ofwhich are incorporated herein by reference.

In another embodiment, the polymers suitable for the present disclosuremay be non-conjugated polymers. The nonconjugated polymer may be thebackbone with all functional groups on the side chain. Examples of suchnonconjugated polymers for use as phosphorescent host or phosphorescentemitter materials may be found in patent applications such as U.S. Pat.No. 7,250,226 B2, JP2007059939A, JP2007211243A2 and JP2007197574A2.Examples of such nonconjugated polymers used as fluorescentlight-emitting materials may be found in the patent applicationsJP2005108556, JP2005285661, and JP2003338375. In addition, thenon-conjugated polymer may also be a polymer, with the conjugatedfunctional units on the backbone linked by non-conjugated linking units.Examples of such polymers are disclosed in DE102009023154.4 andDE102009023156.0. The whole contents of the above mentioned patentdocuments are incorporated herein by reference.

In some embodiments, the metal organic complex is present in an amountof from 0.01 to 30 wt %, preferably from 0.1 to 20 wt %, more preferablyfrom 0.2 to 15 wt %, most preferably from 2 to 15 wt %, based on themixture of the present disclosure.

In a preferred embodiment, the mixture according to the presentdisclosure comprises an organic metal complex according to the presentdisclosure and the triplet host material as described above.

In another preferred embodiment, the mixture according to the presentdisclosure comprises a metal organic complex according to the presentdisclosure, the triplet host material as described above and anotherorganic metal complex.

The present disclosure further relates to a formulation comprising theorganic metal complex or the polymer or the mixture, and at least oneorganic solvent. The present disclosure further relates to a filmcomprising the organic metal complex or the polymer according to thepresent disclosure prepared from solution.

Examples of the organic solvents include, but not limited to, methanol,ethanol, 2-methoxyethanol, dichloromethane, trichloromethane,chlorobenzene, o-dichlorobenzene, tetrahydrofuran, anisole, morpholine,toluene, o-xylene, m-xylene, p-xylene, 1,4-dioxahexane, acetone, methylethyl ketone, 1,2-dichloroethane, 3-phenoxytoluene,1,1,1-trichloroethane, 1,1,2,2-tetrachloroethane, ethyl acetate, butylacetate, dimethylformamide, dimethylacetamide, dimethyl sulfoxide,tetrahydronaphthalene, naphthane, indene and/or their mixtures.

In a preferred embodiment, the formulation according to the presentdisclosure is a solution.

In another preferred embodiment, the formulation according to thepresent disclosure is a suspension.

The formulation in the examples of the present disclosure may comprisean organic metal complex or a polymer or their mixture from 0.01 to 20wt %, more preferably from 0.1 to 15 wt %, more preferably from 0.2 to10 wt %, and most preferably from 0.25 to 5 wt %.

The present disclosure also relates to the use of said formulation as acoating or printing ink in the preparation of organic electronicdevices, and particularly preferably by means of printing or coating ina preparation process.

Among them, suitable printing or coating techniques may include, but notlimited to, ink-jet printing, nozzle printing, typography, screenprinting, dip coating, spin coating, blade coating, roll printing,torsion printing, lithography, flexography, rotary printing, spraycoating, brush coating or pad printing, slit type extrusion coating, andso on. Preferred are gravure printing, slit type extrusion coating,nozzle printing and inkjet printing. The solution or suspension mayadditionally comprise one or more components such as surface activecompounds, lubricants, wetting agents, dispersing agents, hydrophobicagents, binders, etc., for adjusting viscosity, film forming properties,improving adhesion, and the like. For more information about printingtechniques and their requirements for solutions, such as solvent,concentration, viscosity, etc., see Handbook of Print Media:Technologies and Production Methods, edited by Helmut Kipphan, ISBN3-540-67326-1.

Based on the above polymers, the present disclosure also providesapplication of the organic metal complexes or polymers as describedabove in an organic electronic device, which may be selected from, butnot limited to, organic light emitting diodes (OLED), organicphotovoltaics (OPVs), organic light emitting electrochemical cells(OLEEC), organic field effect transistor (OFET), organic light emittingfield effectors, organic lasers, organic spintronic devices, organicsensors, and organic plasmon emitting diodes, especially OLED. In anembodiment of the present disclosure, the organic metal polymer ispreferably used in a light-emitting layer of a OLED device.

The present disclosure further provides an organic electronic devicewhich may comprise at least one organic metal complex or polymer asdescribed above. Typically, such an organic electronic device maycomprise at least a cathode, an anode, and a functional layer betweenthe cathode and the anode, wherein the functional layer may comprise atleast one organic metal complex as described above. The organicelectronic device may be selected from, but not limited to, organiclight emitting diodes (OLED), organic photovoltaics (OPVs), organiclight emitting electrochemical cells (OLEEC), organic field effecttransistor (OFET), organic light emitting field effectors, organiclasers, organic spintronic devices, organic sensors, and organic plasmonemitting diodes.

In a particularly preferred embodiment, the organic electronic device,especially OLED may include a substrate, an anode, at least onelight-emitting layer, and a cathode.

The substrate may be opaque or transparent. Transparent substrates maybe used to make transparent light-emitting components. See, for example,Bulovic et al., Nature 1996, 380, p 29, and Gu et al., Appl. Phys. Lett.1996, 68, p 2606. The substrate may be rigid or flexible. The substratemay be plastic, metal, semiconductor wafer or glass. Most preferably thesubstrate has a smooth surface. Substrates free of surface defects areparticularly desirable. In a preferred embodiment, the substrate isflexible and may be selected from polymer films or plastic, with a glasstransition temperature (Tg) of 150° C. or above, more preferably above200° C., more preferably above 250° C., and most preferably above 300°C. Examples of suitable flexible substrates are poly (ethyleneterephthalate) (PET) and polyethylene glycol (2,6-naphthalene) (PEN).

The anode may comprise a conductive metal or a metal oxide, or aconductive polymer. The anode may easily inject holes into thehole-injection layer (HIL) or the hole-transport layer (HTL) or thelight-emitting layer. In one embodiment, the absolute value of thedifference between the work function of the anode and the HOMO energylevel or the valence band energy level of the emitter in thelight-emitting layer or of the p-type semiconductor material of the HILor HTL or the electron-blocking layer (EBL) may be smaller than 0.5 eV,more preferably smaller than 0.3 eV, and most preferably smaller than0.2 eV. Examples of anode materials may include, but not limited to, Al,Cu, Au, Ag, Mg, Fe, Co, Ni, Mn, Pd, Pt, ITO, aluminum-doped zinc oxide(AZO), and the like. Other suitable anode materials are known and may bereadily selected for use by a person skilled in the art. The anodematerial may be deposited using any suitable technique, such as suitablephysical vapor deposition, including RF magnetron sputtering, vacuumthermal evaporation, electron beam (e-beam), and the like. In someembodiments, the anode may be patterned. The patterned ITO conductivesubstrate is commercially available and may be used to fabricate thedevice according to the disclosure.

The cathode may comprise a conductive metal or a metal oxide. Thecathode may easily inject electrons into the EIL or ETL or directly intothe light-emitting layer. In one embodiment, the absolute value of thedifference between the work function of the cathode and the LUMO energylevel or the valence band energy level of the emitter in thelight-emitting layer or of the n-type semiconductor material of theelectron-injection layer (EIL) or the electron-transport layer (ETL) orthe hole-blocking layer (HBL) may be smaller than 0.5 eV, morepreferably smaller than 0.3 eV, and most preferably smaller than 0.2 eV.In principle, all of the material that may be used as the cathode of anOLED may serve as a cathode material for the device of the presentdisclosure. Examples of the cathode material may include, but notlimited to, Al, Au, Ag, Ca, Ba, Mg, LiF/Al, MgAg alloys, BaF2/AI, Cu,Fe, Co, Ni, Mn, Pd, Pt, ITO, and the like. The cathode material may bedeposited using any suitable technique, such as suitable physical vapordeposition, including RF magnetron sputtering, vacuum thermalevaporation, electron beam (e-beam), and the like.

OLEDs may also comprise other functional layers such as hole-injectionlayer (HIL), hole-transport layer (HTL), electron-blocking layer (EBL),electron-injection layer (EIL), electron-transport layer (ETL), andhole-blocking layer (HBL). Materials suitable for use in thesefunctional layers are described in detail as before.

In a preferred embodiment, in the light emitting device according to thepresent disclosure, the light-emitting layer thereof comprises theorganic metal complex or polymer of the present disclosure and may beprepared by a solution processing method.

The light emitting device according to the present disclosure may have alight emission wavelength between 300 and 1000 nm, more preferablybetween 350 and 900 nm, and more preferably between 400 and 800 nm.

The present disclosure also relates to the use of organic electronicdevices according to the present disclosure in a variety of electronicdevices including, but not limited to, display devices, lightingdevices, light sources, sensors, and the like.

The disclosure will now be described with reference to the preferredembodiments, but the disclosure is not to be construed as being limitedto the following examples. It is to be understood that the appendedclaims are intended to cover the scope of the disclosure. A personskilled in the art will understand that modifications can be made tovarious embodiments of the present disclosure with the teaching of thepresent disclosure, which will be covered by the spirit and scope of theclaims of the disclosure.

EXAMPLES

1. Metal Organic Complexes and their Energy Structures

The energy level of the metal organic complex Ir-1-Ir-5 can be obtainedby quantum computation, for example, by using TD-DFT (time-dependentdensity functional theory) by Gaussian03W (Gaussian Inc.), and specificsimulation methods can be found in WO2011141110. First, the moleculargeometry is optimized by semi-empirical method “GroundState/Hartree-Fock/Default Spin/LanL2MB” (Charge 0/Spin Singlet), andthen the energy structure of organic molecules is determined by TD-DFT(time-dependent density functional theory) Count “TD-SCF/DFT/DefaultSpin/B3PW91/gen geom=communication pseudo=lanl2” (Charge 0/SpinSinglet). The HOMO and LUMO energy levels are calculated using thefollowing calibration formula, and S1 and T1 are used directly.HOMO(eV)=((HOMO(Gaussian)×27.212)−0.9899)/1.1206LUMO(eV)=((LUMO(Gaussian)×27.212)−2.0041)/1.385

Wherein, HOMO (G) and LUMO (G) are the direct results of Gaussian 03W,in units of Hartree. The results are shown in Table 1:

TABLE 1 Materials HOMO [eV] LUMO [eV] T1 [eV] S1 [eV] Ir-1 −5.18 −2.472.59 2.70 Ir-2 −5.33 −2.77 2.39 2.47 Ir-3 −5.47 −3.04 2.13 2.25 Ir-4−5.04 −2.80 2.01 2.09 Ir-5 −5.45 −2.67 2.61 2.74

2. Synthesis of the Organic Metal Complexes

The synthesis of metal organic complexes is as follows:

Synthesis of Intermediate 1a

Carbazole (1.67 g, 10 mmol), cuprous iodide (19 mg, 0.1 mmol), potassiumcarbonate (2.76 g, 0.02 mol), 2-bromopyridine (1.896 g, 0.012 mol) andDMF 20 mL were refluxed for 24 h under nitrogen and then cooled to roomtemperature. Water was added to the reaction solution, and then thereaction solution was extracted with ethyl acetate. The organic phasewas washed with water, then dried with anhydrous magnesium sulfate,concentrated, and recrystallized from ethanol to give 1a (1.5 g).

Synthesis of Intermediate 1b

The intermediate 1a (0.39 g, 1.6 mmol) and iridium trichloride hydrate(0.23 g, 0.66 mmol) were put in a dry two-necked flask. Then thetwo-necked flask was evacuated then filled with nitrogen, which wasrepeated three times, followed by the addition of a mixture solution of10 mL of ethylene glycol monoethyl ether and 3 mL of water. The reactionsolution was stirred at 110° C. for 24 hours, then cooled to roomtemperature, filtered, washed with n-hexane and dried, without furtherpurification.

Synthesis Example 1: Synthesis of Compound Ir-1

The intermediate 1b (0.14 g, 0.1 mmol), acetylacetone (0.1 mL, 1 mmol)and Na₂CO₃ (0.106 g, 1 mmol) were placed in a dry two-necked flask. Thenthe two-necked flask was evacuated then filled with nitrogen, which wasrepeated three times, followed by the addition of 10 mL ethylene glycolmonoethyl ether. The reaction solution was stirred under refluxovernight, then cooled to room temperature, followed by the addition ofwater. Then the reaction solution was extracted with dichloromethane,then dried, concentrated and purified by column chromatography withdichloromethane to give Ir-1 (0.03 g).

Synthesis of Intermediate 2a

Carbazole (1.67 g, 10 mmol), cuprous iodide (19 mg, 0.1 mmol), potassiumcarbonate (2.76 g, 0.02 mol), 2-chloropyrimidine (1.368 g, 0.012 mol)and DMF 20 mL were refluxed for 24 h under nitrogen and then cooled toroom temperature. Water was added to the reaction solution, and then thereaction solution was extracted with ethyl acetate. The organic phasewas washed with water, dried with anhydrous magnesium sulfate,concentrated, and recrystallized from ethanol to give 2a (1.5 g).

Synthesis of intermediate 2b

The intermediate 2a (0.39 g, 1.6 mmol) and iridium trichloride hydrate(0.23 g, 0.66 mmol) were placed in a dry two-necked flask. Then the drytwo-necked flask was evacuated then filled with nitrogen, which wasrepeated three times, followed by the addition of a mixture solution of10 mL of ethylene glycol monoethyl ether and 3 mL of water. The reactionsolution was stirred at 110° C. for 24 hours, cooled to roomtemperature, filtered, washed with n-hexane and dried, without furtherpurification.

Synthesis Example 2: Synthesis of Compound Ir-2

The intermediate 2b (0.14 g, 0.1 mmol), acetylacetone (0.1 mL, 1 mmol),Na₂CO₃ (0.106 g, 1 mmol) were placed in a dry two-necked flask. Then thetwo-necked flask was evacuated then filled with nitrogen, which wasrepeated three times, followed by the addition of 10 mL ethylene glycolmonoethyl ether. The reaction solution was stirred under refluxovernight, then cooled to room temperature, followed by the addition ofwater. Then the reaction solution was extracted with dichloromethane,then dried, concentrated and purified by column chromatography withdichloromethane to give Ir-2 (0.025 g).

Synthesis of Intermediate 3a

Carbazole (0.67 g, 10 mmol), cuprous iodide (19 mg, 0.1 mmol), potassiumcarbonate (2.76 g, 0.02 mol), 2-chloropyrazine (1.368 g, 0.012 mol) andDMF 20 mL were refluxed for 24 h under nitrogen and then cooled to roomtemperature. Water was added to the reaction solution, and then thereaction solution was extracted with ethyl acetate. The organic phasewas washed with water, then dried with anhydrous magnesium sulfate,concentrated, and then recrystallized from ethanol to give 2a (1.5 g).

Synthesis of Intermediate 3b

The intermediate 3a (0.39 g, 1.6 mmol) and iridium trichloride hydrate(0.23 g, 0.66 mmol) were placed in a dry two-necked flask. Then thetwo-necked flask was evacuated then filled with nitrogen, which wasrepeated three times, followed by the addition of a mixture solution of10 mL of ethylene glycol monoethyl ether and 3 mL of water. Then thereaction solution was stirred at 110° C. for 24 hours, cooled to roomtemperature, filtered, washed with n-hexane and dried, without furtherpurification.

Synthesis Example 3: Synthesis of Compound Ir-3

The intermediate 3b (0.14 g, 0.1 mmol), acetylacetone (0.1 mL, 1 mmol)and Na₂CO₃ (0.106 g, 1 mmol) were placed in a dry two-necked flask. Thenthe two-necked flask was evacuated then filled with nitrogen, which wasrepeated three times, followed by the addition of 10 mL ethylene glycolmonoethyl ether, stirred under reflux overnight, cooled to roomtemperature, followed by the addition of water. Then the reactionsolution was extracted with dichloromethane, then dried, concentratedand purified with dichloromethane to give Ir-3 (0.025 g).

Synthesis of Intermediate 4a

Carbazole (1.67 g, 10 mmol), cuprous iodide (19 mg, 0.1 mmol), potassiumcarbonate (2.76 g, 0.02 mol), 3,6-dichloropyrazine (1.788 g, 0.012 mol)and DMF 20 mL were refluxed under nitrogen for 24 h, and then cooled toroom temperature. Water was added to the reaction solution, and then thereaction solution was extracted with ethyl acetate. The organic phasewas washed with water, then dried anhydrous magnesium sulfate,concentrated, and then recrystallized from ethanol to give 4a (1.45 g).

Synthesis of intermediate 4b

The intermediate 4a (0.81 g, 2.9 mmol) and cuprous iodide (19 mg, 0.1mmol) were placed in a dry two-necked flask. Then the two-necked flaskwas evacuated then filled with nitrogen, which was repeated three times,followed by the addition of 10 mL of dry THF. The reaction solution wasstirred at 0° C. for 20 minutes, then tBuMgCl (7 mL, 1 M THF solution, 7mmol) was added and the reaction was continued under stirring at 0° C.for 2 h, then diluted with tert-butanol methyl ether and quenched withdilute hydrochloric acid. The organic phase was washed with chlorinatedammonium solution, sodium bicarbonate solution and water in succession,then dried over anhydrous magnesium sulfate, concentrated, and thenpassed through a silica gel column to give 4b (0.7 g).

Synthesis of Intermediate 4c

The intermediate 4b (0.48 g, 1.6 mmol), iridium trichloride hydrate(0.23 g, 0.66 mmol) was placed in a dry two-necked flask. Then thetwo-necked flask was evacuated then filled with nitrogen, which wasrepeated three times, followed by the addition of a mixture solution of10 mL of ethylene glycol monoethyl ether and 3 mL of water. The reactionsolution was stirred at 110° C. for 24 hours, cooled to roomtemperature, filtered, washed with n-hexane and dried, without furtherpurification.

Synthesis Example 4: Synthesis of Compound Ir-4

The intermediate 4c (0.165 g, 0.1 mmol), acetylacetone (0.1 mL, 1 mmol)and Na₂CO₃ (0.106 g, 1 mmol) were placed in a dry two-necked flask. Thenthe two-necked flask was evacuated then filled with nitrogen, which wasrepeated three times, followed by the addition of 10 mL ethylene glycolmonoethyl ether. The reaction solution was stirred under refluxovernight, cooled to room temperature, followed by the addition ofwater. The reaction solution was extracted with dichloromethane, thendried, concentrated and purified by passing through dichloromethane togive Ir-4 (0.025 g).

Synthesis of Intermediate 5a

Trichlorotriazine (5.35 g, 29 mmol) and cuprous iodide (190 mg, 1 mmol)were placed in a dry two-necked flask. Then the two-necked flask wasevacuated then filled with nitrogen, which was repeated three times,followed by the addition of 20 mL of dry THF. After stirring for 20minutes at 0° C., tBuMgCl (70 mL, 1 M THF solution, 70 mmol) was addedand the reaction was continued at 0° C. for 2 h under stirring. Then thereaction was diluted with tert-butanol methyl ether and quenched withdilute hydrochloric acid. The organic phase was washed with ammoniumchloride solution, sodium bicarbonate solution and water in succession,then dried over anhydrous magnesium sulfate, concentrated, and thenpassed through a silica gel column to give 5a (5.8 g).

Synthesis of Intermediate 5b

Carbazole (1.67 g, 10 mmol), cuprous iodide (19 mg, 0.1 mmol), potassiumcarbonate (2.76 g, 0.02 mol), intermediate 5a (2.72 g, 0.012 mol) andDMF 20 mL were refluxed under nitrogen for 24 h, and then cooled to roomtemperature. Water was added to the reaction solution and the reactionsolution was extracted with ethyl acetate. The organic phase was washedwith water, dried over anhydrous magnesium sulfate, concentrated, andthen recrystallized from ethanol to give 5b (2.8 g).

Synthesis of Intermediate 5c

The intermediate 5b (0.57 g, 1.6 mmol) and iridium trichloride hydrate(0.23 g, 0.66 mmol) were placed in a dry two-necked flask. Then thetwo-necked flask was evacuated then filled with nitrogen, which wasrepeated three times, followed by the addition of a mixture solution of10 mL of ethylene glycol monoethyl ether and 3 mL of water. The reactionsolution was stirred at 110° C. for 24 hours, cooled to roomtemperature, filtered, washed with n-hexane and dried, without furtherpurification.

Synthesis Example 5: Synthesis of Compound Ir-5

The intermediate 5c (0.188 g, 0.1 mmol), acetylacetone (0.1 mL, 1 mmol),Na₂CO₃ (0.106 g, 1 mmol) were placed in a dry two-necked flask. Then thetwo-necked flask was evacuated then filled with nitrogen, which wasrepeated three times, followed by the addition of 10 mL ethylene glycolmonoethyl ether. The reaction solution was stirred under refluxovernight, cooled to room temperature, followed by the addition ofwater. The reaction solution was extracted dichloromethane, then dried,concentrated and purified with dichloromethane column to give Ir-5(0.038 g).

3. Preparation and Characterization of OLED Devices:

The preparation steps of OLED devices having ITO/NPD (60 nm)/15% Ir-1 toIr-5: mCP (15 nm)/TPBi (65 nm)/LiF (1 nm)/Al (150 nm)/cathode are asfollows:

a. cleaning of a conductive glass substrate: when used for the firsttime, a variety of solvents may be used for cleaning, such aschloroform, ketone, isopropyl alcohol, and then UV ozone plasmatreatment was carried out;

b. HTL (60 nm), EML (25 nm), ETL (65 nm): by hot vapor deposition inhigh vacuum (1×10-6 mbar, mbar);

c. cathode: LiF/Al (1 nm/150 nm) being prepared by hot vapor depositionin high vacuum (1×10⁶ mbar);

d. package: device was packaged with UV curing resin in the nitrogenglove box.

The current-voltage-luminance (JVL) characteristics of each OLED deviceare characterized by characterization equipment, while importantparameters such as efficiency and external quantum efficiency wererecorded. After detection, maximum external quantum efficiency of OLEDx(corresponding to metal organic Ir-x) reaches more than 10%.

Further optimization, such as device structure optimization,optimization for HTM, ETM and the combination of the host material, willfurther improve the performance of the device, especially theefficiency, drive voltage and life.

It is to be understood that the application of the present disclosure isnot limited to the above-described examples and that a person skilled inthe art may make improvement or modification in accordance with theabove description, all of which are within the scope of the claimsappended hereto.

What is claimed is:
 1. An organic metal complex, represented by thefollowing general formula (I) or (II):

wherein, X is a single bond, X is linked to Ar³ or Ar² by a single bond;each of Ar¹-Ar³ is the same or different from one another in multipleoccurrences, and is an unsubstituted or a R¹-substituted aromatichydrocarbon or heteroaromatic cyclic hydrocarbon system; each R¹ is thesame or different from one another in multiple occurrences, and R¹ isselected from the group consisting of H; F; Cl; Br; I; D; CN; NO₂; CF₃;B(OR²)₂; Si(R²)₃; straight-chain alkanes; alkane ethers; alkanethioethers, branched alkanes or cycloalkanes containing 1 to 10 carbonatoms; and alkane ethers or alkane thioether groups containing 3 to 10carbon atoms; each R¹ group is substituted with one or more activegroups R², and one or more non-adjacent methylene groups (CH₂) areoptionally substituted by any one selected from the group consisting ofR²C═CR², C═C, Si(R²)₂, Ge(R²)₂, Sn(R²)₂, C═O, C═S, C═Se, C═N(R²), O, S,—COO— and CONR²; wherein one or more H can be substituted by D, F, Cl,Br, I, CN or N₂; or by an aromatic amine substituted by one or more R²or one aromatic or heteroaromatic group, or by a substituted orunsubstituted carbazole; each R² is the same or different from oneanother in multiple occurrences, and is selected from the groupconsisting of H, D, an aliphatic alkane having 1 to 10 carbons atoms, anaromatic hydrocarbon, and a substituted or unsubstituted aromatic ringor heteroaromatic group having 5 to 10 carbon atoms;

is a single anion ligand, and is independently selected from thefollowing general formulas in multiple occurrences:

wherein each of R⁶⁰ to R¹²⁹ independently represents any one selectedfrom the group consisting of —H; —F; —Cl; Br; I; -D; —CN; —NO₂; —CF₃;B(OR²)₂; Si(R²)₃; straight-chain alkane; alkane ether; alkane thioether,branched alkane or cycloalkane containing 1 to 10 carbon atoms; alkaneether or alkane thioether group containing 3 to 10 carbon atoms, andaryl group containing 6 to 10 carbon atoms, wherein the dashed lineindicates connecting with the metal element M in the form of a singlebond; M is a transitional metal element; m is any one of numbers 1-3,and n is any one of numbers 1-3.
 2. The organic metal complex of claim1, wherein the organic metal complex has a general formula selected fromthe group consisting of:

wherein each of R³, and R⁴ independently represents any one selectedfrom the group consisting of —H; —F; —Cl; Br; I; -D; —CN; —NO₂; —CF₃;B(OR²)₂; Si(R²)₃; straight-chain alkane; alkane ether; alkane thioether,branched alkane, or cycloalkane containing 1 to 10 carbon atoms; alkaneether or alkane thioether group containing 3 to 10 carbon atoms; andaryl group containing 6 to 10 carbon atoms.
 3. The organic metal complexof claim 1, wherein M is selected from the group consisting of Cr, Mo,W, Ru, Rh, Ni, Ag, Cu, Zn, Pd, Au, Os, Re, Ir and Pt.
 4. The organicmetal complex of claim 1, wherein M is selected from Ir or Pt.
 5. Theorganic metal complex of claim 1, wherein

is N-hetero-six-membered ring unit, and is independently selected fromgeneral formulas C1 to C5 in multiple occurrences:

wherein each of R⁷ to R¹⁰ independently represents any one selected fromthe group consisting of —H; —F; —Cl; Br; I; -D; —CN; —NO₂; —CF₃;B(OR²)₂; Si(R²)₃; straight-chain alkane; alkane ether; alkane thioether,branched alkane or cycloalkane containing 1 to 10 carbon atoms; alkaneether or alkane thioether group containing 3 to 10 carbon atoms, andaryl group containing 6 to 10 carbon atoms.
 6. The organic metal complexof claim 1, wherein the light emission wavelength is between 300 and1000 nm.
 7. A mixture comprising the organic metal complex of claim 1and further at least one organic functional material which is any oneselected from a hole-injecting material, a hole-transporting material,an electron-transporting material, an electron-injecting material, anelectron-blocking material, a hole-blocking material, a light emittermaterial, and a host material.
 8. The mixture of claim 7, comprising theorganic metal complex with a weight percentage from 0.01 to 30 wt %. 9.The mixture of claim 7, further comprising a triplet host material. 10.The mixture of claim 7, further comprising a triplet host material andanother organic metal complex.
 11. A formulation comprising the organicmetal complex of claim 1, and at least one organic solvent.
 12. Theformulation of claim 11, wherein the organic solvent is selected fromthe group consisting of methanol, ethanol, 2-methoxyethanol,dichloromethane, trichloromethane, chlorobenzene, o-dichlorobenzene,tetrahydrofuran, anisole, morpholine, toluene, o-xylene, m-xylene,p-xylene, 1,4-dioxahexane, acetone, methyl ethyl ketone,1,2-dichloroethane, 3-phenoxytoluene, 1,1,1-trichloroethane,1,1,2,2-tetrachloroethane, ethyl acetate, butyl acetate,dimethylformamide, dimethylacetamide, dimethyl sulfoxide,tetrahydronaphthalene, naphthane, indene and/or a combination thereof.13. The formulation of claim 11, wherein the formulation comprises theorganic metal complex in weight percentage from 0.01 to 20%.
 14. Theformulation of claim 11, wherein the formulation comprises the organicmetal complex in weight percentage from 0.01 to 15%.
 15. The formulationof claim 11, wherein the formulation comprises the organic metal complexin weight percentage from 0.2 to 10%.
 16. The formulation of claim 11,wherein the formulation comprises the organic metal complex in weightpercentage from 0.25 to 5%.
 17. The organic metal complex of claim 1,wherein the light emission wavelength is between 350 and 900 nm.
 18. Theorganic metal complex of claim 1, wherein the light emission wavelengthis between 400 and 800 nm.
 19. The organic metal complex of claim 1,wherein M is Pt.